The instant invention provides branched chain olefin dioxolanes, dithiolanes and oxathiolanes which are used to augment or enhance the aroma and/or taste of consumable materials including foodstuffs, chewing gums, medicinal products, toothpastes, chewing tobaccos, perfume compositions, colognes, perfumed articles, smoking tobaccos and smoking tobacco articles.
Materials which can provide pleasant cedar, amber, woody, sweet, patchouli-like fragrance notes are known in the art of perfumery. Many of the natural materials which provide such fragrances and contribute desired nuances to perfumery compositions are high in cost, vary in quality from one batch to another and/or are generally subject to the usual variations of natural products.
There is, accordingly, a continuing effort to find synthetic materials which will replace the essential fragrance notes provided by natural essential oils or compositions thereof. Unfortunately, many of the synthetic materials either have the desired nuances only to a relatively small degree or else contribute undesirable or unwanted odor to the composition. The search for materials which can provide a more refined patchouli-like fragrance has been difficult and relatively costly in the areas of both natural products and synthetic products.
In addition, artificial flavoring agents for foodstuffs have received increasing attention in recent years. In many places such food flavoring agents have been preferred over natural flavoring agents at least in part due to their diminished cost and their reproducible flavor qualities. For example, natural food flavoring agents such as extracts, concentrates and the like are often subject to wide variations due to changes in the quality, type and treatment of the raw materials.
Such variations can be reflected in the end product and result in unfavorable flavor characteristics in said end product. Additionally, the presence of the natural product in the ultimate food may be undesirable because of increased tendency to spoil. This is particularly troublesome in food and food uses where such products as dips, soups, chips sausages, gravies and the like are apt to be stored prior to use.
The fundamental problem in creating artificial flavoring agents is that the artificial flavor to be achieved be as natural as possible. This generally proves to be a difficult task since the mechanism for flavor development in many foods is not completely known. This is particularly noticable in products having nutty, earthy, woody-balsamic, fresh walnut kernel and walnut skin flavor characteristics.
Reproduction of nutty, earthy, woody-balsamic, fresh walnut kernel and walnut skin flavor and aroma has been the subject of long and continuing searches by those engaged in the production of foodstuffs and beverages. The severe shortages of food in many parts of the world has given rise to the development of previously unused sources of protein which are unpalatable. Accordingly, the need has arisen for the use of flavoring materials which will make such sources of protein palatable to human sensory organs.
Furthermore, chemical compounds which can provide sweet, woody, vetiver and cedar-like aroma and taste nuances to smoking tobacco both prior to and on smoking in both the main stream and the side stream particularly where black tobacco aroma and taste nuances are desired and natural cigar-like taste nuances are desirable in the art of smoking tobacco aromatization. Many of the natural materials which provide such aroma and taste nuances are high in cost, unobtainable at times, vary in quality from one batch to another and/or are generally subject to the usual variations of natural products.
U.S. Pat. No. 3,760,303 (1971) discloses the cyclic acetal of 2,4-hexadienal with ethylene glycol and discloses its use in the bouquet of citrus-type odorant formulations. This compound has the structure: ##STR2##
Netherlands published application No. 6,406,295 (1965) discloses gamma, delta-unsaturated aldehyde derivatives for use as perfumes, for example in soaps. These derivatives are cyclic acetals and have the structures: ##STR3## wherein R is hydrogen or methyl.
German Offenlegungschrift No. 2,103,567 (1971) discloses the use as perfumes of 2-(1-alkyl-2-alkenyl)-1,3-dioxolanes having the structure: ##STR4##
In the Federal Register 31,7563 (May 26, 1966) and in Chem. Abstracts 62, 11055e the compound having the structure: ##STR5## is disclosed to be useful as a synthetic food flavoring substance.
Beilstein, Vol. E II19 at page 16:5(2) discloses 2-(1-methyl-1-butenyl)1,3-dioxolane having the structure: ##STR6## The Beilstein Abstract summarizes the article by Hibert et al. J. Am. Chem. Soc. 51 (1929) page 611 (Title: "Studies on Reactions Relating to Carbohydrates and Polysaccharides. XX. Comparison of Tendencies of Saturated and Unsaturated Aldehydes Toward Cyclic Acetal Formation"). This compound is shown to be prepared by reacting alpha methyl beta ethyl acrolein with ethylene glycol using a 40% sulfuric acid catalyst. The compound is indicated to have a boiling point of 170.degree.-174.degree. C. at 12 mm Hg pressure.
2-(1-ethyl-1-pentenal)-1,3-dioxolane and 2-(1-propenyl)-4-methyl-1,3-dioxolane are shown to be prepared by Heywood and Phillips, J. Org. Chem. 25 (1960) page 1699 entitled: "The Oxidation of Unsaturated Acetals and Acylals With Peracetic Acid".
None of the foregoing references discloses or implies the subject matter of the instant invention.
Furthermore, various heterocyclic compounds containing three, four or five sulfur atoms in the ring have been said to be flavorful or aroma-imparting. Thus, Chang et al in Chemistry and Industry for Nov. 23, 1968, pages 1639-1641, identified, 3,5-dimethyl-1,2,4-trithiolane in the volatile flavor compounds of boiled beef; and Wada et al in U.S. Pat. No. 3,503,758 issued on Mar. 31, 1970, describes pentathiepane and various tetrathiepanes as having a good aroma and, therefore, useful as flavor enhancers. The tetra- and pentathiepanes possess a sweet, meaty flavor. Polyalkyl symmetrical trithianes have been disclosed in copending U.S. application Ser. No. 166,683 filed July 28, 1971, as having a sweet, nutty aroma and taste and suitable for fruit, net and meat flavors.
Five or six membered heterocyclic compounds having two sulfur atoms in the ring are disclosed to be useful in altering the flavor or aroma of foodstuffs in U.S. application Ser. No. 272,396 filed on July 17, 1972. Such dithio heterocyclic compounds in that case include dithiolanes and dithianes, which may be alkyl substituted or non-alkyl substituted. According to U.S. application Ser. No. 272,396, dithio heterocyclic compounds found suitable are represented by one of the following formulae: ##STR7## and each of R.sub.1 to R.sub.4 is hydrogen or a lower alkyl radical of 1 to 3 carbon atoms.
Although a number of meta-dioxanes and meta-dioxolanes are indicated in the prior art to have specific organoleptic properties, such properties of the meta-dioxanes and meta-dioxolanes are different in kind from the aromas and tastes of the heterocyclic oxathio compounds of our invention. Thus, German Offenlegungschrift 2,233,245 discloses 1,3 dioxolanes of the formula: ##STR8## wherein R.sub.1 or R.sub.2 can be, interalia, ethyl or propyl as baked goods aromas.
Beilstein discloses the following:
______________________________________ Compound Organoleptic Structure Reference Property ______________________________________ ##STR9## E II 19:10 Camphor-like smelling liquid ##STR10## E II 19:10 Liquid of camphor- type odor ##STR11## E II 19:12 Ether-like smelling oil ##STR12## E II 19:12 Liquid of camphor- like smell ##STR13## E II 19:12 Camphor-type smelling liquid ##STR14## E II 19:12 Liquid of pleasant, camphor-like aroma ##STR15## E II 19:12 Camphor-like smelling liquid ##STR16## E II 19:13 Liquid of intense camphor-like odor ##STR17## E II 19:14 Liquid with camphor- like odor ##STR18## E II 19:14 Liquid with camphor- like odor (impure) ##STR19## E II 19:14 Liquid with intense odor, reminiscent of heptanal ##STR20## E I 19:609 Acetal-like smelling liquid ______________________________________ Chem. Abstracts 69; 96605 Z discloses the following organoleptic properties for various metadioxanes: Compound Organoleptic Structure Property ______________________________________ ##STR21## Strong, vegetables ##STR22## Strong, grassy, jasmine ##STR23## Strong, vegetable ##STR24## Strong, grassy, jasmine ##STR25## Strong, jasmine ##STR26## Strong, jasmine ##STR27## Medium, jasmine ##STR28## Strong, sharp, vegetables ##STR29## Strong, jasmine ##STR30## Strong, musty, slightly chilly ##STR31## Medium, musty, slightly chilly ##STR32## Medium, musty, mushroom ##STR33## Medium, vegetables, flower note ##STR34## Weak; gardenia scent ______________________________________
Furthermore, in accordance with the disclosure of U.S. Pat. No. 4,031,257, it was found that certain 5 or 6 membered heterocyclic compounds having one sulfur atom and one oxygen atom in the ring (hereinafter called "oxathio heterocyclic compounds"), a number of which are novel compounds, are useful in altering, modifying or enhancing the flavor or aroma of a foodstuff, chewing gum or medicinal product. Such oxathio heterocyclic compounds include oxathiolanes and oxathianes, which may be alkyl substituted, carboxyalkyl substituted and/or acyl substituted. The oxygen atom and the sulfur atom in the ring are separated by one carbon atom. Thus, the oxathio heterocyclic compounds found suitable according to this invention may be represented by the following formula: ##STR35## wherein n is 0 or 1; R.sub.1 is hydrogen or C.sub.1 -C.sub.9 alkyl; R.sub.2 is hydrogen, lower alkyl, aryl, carboalkoxy or alkanoyl; or R.sub.1 and R.sub.2 taken together complete a carbocyclic ring having from five up to nine carbon atoms; R.sub.3 and R.sub.4 are the same or different and are each hydrogen or lower alkyl; with the sum of the carbon atoms in R.sub.1, R.sub.2, R.sub.3 and R.sub.4 being greater than or equal to 1; and the sum of the carbon atoms in R.sub.1 and R.sub.2 being less than or equal to nine.
Furthermore, it is disclosed in U.S. Pat. No. 4,159,347 that solid and liquid foodstuff, chewing gum, medicinal product and toothpaste compositions and flavoring compositions therefor having sweet, fruity, gooseberry, green, aniseed, licorice, floral and herbal aroma characteristics and sweet, fruity, gooseberry, green, spearmint, aniseed, licorice, floral and herbal flavor characteristics with albedo-like nuances may be provided by the utilization of cyclic acetals of 2-methyl-2-pentenal having the generic structure: ##STR36## wherein R is selected from the group consisting of hydrogen and methyl and the wavy lines represent covalent bonds, and signify a "cis" or "trans" configuration of the dioxolane moiety with respect to the ethyl moiety; each moiety being bonded to the ethenyl group of the molecule.
Oxathiolanes, dioxolanes and dithiolanes are described in the following publication:
U.S. Pat. No. 4,042,601 PA1 U.S. Pat. No. 3,863,013
However, nothing existing in the prior art discloses the compounds described by the generic structure: ##STR37## wherein R.sub.1 represents C.sub.1 -C.sub.3 lower alkyl; R.sub.2, R.sub.3, R.sub.4 and R.sub.5 represent the same or different hydrogen or C.sub.1 -C.sub.3 lower alkyl; X and Y represent the same or different oxygen or sulfur; and one of the dashed lines represents a carbon-carbon double bond and the other of the dashed lines represent carbon-carbon single bonds.